Tailoring metal-organic framework catalysts by click chemistry.

We successively introduce new catalytic centers through click reaction into MOFs and modify their environment by addition of lipophilic groups. The resulting bifunctionalized MOF provides an optimized balance between basicity and lipophilicity and shows outstanding performance for the transesterification reaction.

Catalysis of transesterification by a nonfunctionalized metal-organic framework: acido-basicity at the external surface of ZIF-8 probed by FTIR and ab initio calculations.

The zeolite imidazolate framework ZIF-8 is shown for the first time to be able to catalyze transesterification of vegetable oil with significant activity. Rationalization of this behavior at the atomic scale is provided by combining CO adsorption monitored by FTIR and DFT calculations (clusters and periodic models). We demonstrate that the acido-basic sites are located at the external surface of the material or at defects, but not in the microporosity of ZIF-8.

A zeolitic material with a three-dimensional pore system formed by straight 12- and 10-ring channels synthesized with an imidazolium derivative as structure-directing agent.

IM-20 is a novel microporous germanosilicate with an interesting zeolitic structure. It has been prepared via the fluoride route with 3-butyl-1-methyl-3H-imidazol-1-ium as the organic structure-directing agent and its structure solved from synchrotron powder X-ray diffraction data. The chemical formula per unit cell is Si(42.

Generic postfunctionalization route from amino-derived metal-organic frameworks.

This study deals with the development of a soft, generic, one-pot postfunctionalization method for metal-organic frameworks (MOFs) starting from compounds with an amino group on the linker. The first step consists of transforming the amino group into azide (N(3)) by an unconventional route using tBuONO and TMSN(3). In the same vessel, the desired functionalized MOF then is obtained by the Huisgen 1,3-dipolar cycloaddition of azides to alkynes, otherwise known as the "click" reaction.

Adsorption of CO(2), CH(4), and N(2) on zeolitic imidazolate frameworks: experiments and simulations.

Experimental measurements and molecular simulations were conducted for two zeolitic imidazolate frameworks, ZIF-8 and ZIF-76. The transferability of the force field was tested by comparing molecular simulation results of gas adsorption with experimental data available in the literature for other ZIF materials (ZIF-69). Owing to the good agreement observed between simulation and experimental data, the simulation results can be used to identify preferential adsorption sites, which are located close to the organic linkers.

IM-19: a new flexible microporous gallium based-MOF framework with pressure- and temperature-dependent openings.

Five metal-organic frameworks (MOFs) based on the same three-dimensional gallium terephthalate network (IM-19) are described, and an incommensurate structure (for the as-synthesized form) as well as two remarkable guest-free polymorphs (open and closed) are highlighted.

Co-templating and modelling in the rational synthesis of zeolitic solids.

A 'co-templating' strategy supported by molecular modelling has been used to prepare, for the first time, silicoaluminophosphates with the SAV and KFI framework topologies, each of which has a three-dimensionally connected pore system with high specific volume.

Extra-large-pore zeolites with two-dimensional channels formed by 14 and 12 rings.

Stable zeolites that have larger pore apertures and a three-dimensional pore topology are of interest because they could be used to adsorb larger molecules, particularly for application in oil refining. Several large-pore zeolitic materials with channels formed by openings of more than 12 rings are known, but all of them have a one-dimensional channel system that limits their use in catalysis. We report the synthesis and some characterizations of IM-12, a thermally stable germanium-containing zeolite that contains the first two-dimensional channel system with extra-large pores formed by 14- and 12-ring channels.